Ultramulsion based hair care compositions

ABSTRACT

The present invention relates to various hair care products containing stable, dispersions of certain high viscosity silicones in certain surfactants; wherein: 
     a. the dispersed silicones, which are insoluble in said surfactant, are oriented by the surfactant such that when dispersed in water they are particularly adept at forming oriented coatings on hair with enhanced substantivity, and 
     b. the particle size of the dispersed silicone is from between about 0.1 and about 10 microns, with a particle size distribution such that from substantially all of the dispersed silicone is within this particle size range. These stable dispersions are described as ULTRAMULSION™ dispersions, which, together with their physical properties, when contained in hair care products, provide these hair care products with distinctive conditioning, moisturizing, protecting, etc. properties where the discontinuous silicone phase functions as a reservoir for various hair treatment substances.

BACKGROUND OF THE INVENTION

The present invention relates to unique hair care compositionscontaining a dispersion of certain silicones in certain surfactants.When added to water these dispersions are stable and are distinct fromsolutions, emulsions and microemulsions. These dispersions are referredto hereinafter as ULTRAMULSION™ dispersions. This trademark is theproperty of Whitehill Oral Technologies, Inc. For further informationregarding ULTRAMULSION™ dispersions, see copending application Ser. No.08/144,778, now U.S. Pat. No. 5,538,667, the disclosure of which ishereby incorporated herein by reference. See also copending patentapplication Ser. Nos. 08/462,203; 08/462,600; 08/463,010; 08/461,698;08/464,403; 08/462,599; and 08/462,930; all filed on Jun. 5, 1996, thedisclosures of which are hereby incorporated by reference.

The ULTRAMULSION™ dispersion based hair care products of the presentinvention exhibit unique and unexpected substantivity to hair whileproviding a reservoir for various lipid or oil soluble hair treatmentingredients resulting in conditioning, moisturizing protecting benefitsto the hair that last for extended periods. This combination of enhancedsubstantivity and the reservoir effect described in detail below arefurther combined with excellent particle size which results in uniquecoatings on hair.

The uniqueness and novelty of the ULTRAMULSION™ dispersion based haircare products of the present invention are more readily appreciated whenthese products are compared to other hair care products.

Human hair becomes soiled due to its contact with the surroundingatmosphere and, to a greater extent, from sebum secreted by thesebaceous glands on the head. The build-up of the sebum causes the hairto have a dirty feel and an unattractive appearance. The soiling of thehair necessitates it be cleaned on a regular basis.

Shampooing the hair cleans it by removing soil and sebum. However, theshampooing process has disadvantages in that the hair is left in a wet,tangled and generally unmanageable state. A variety of approaches havebeen developed to alleviate after-shampoo problems. These range from theinclusion of hair conditioning aids in shampoos to post-shampooapplication of hair conditioners, i.e., hair rinses. Hair rinsestypically work by depositing a cationic material to the hair, e.g., toneutralize the charge to hair and thereby improve wet combing but haveno actual conditioning properties. The conditioning is achieved bycausing less damage to the hair by improved wet combing. Hairconditioning rinses are generally liquid in nature and must be appliedin a separate step following shampooing, left on the hair for a lengthof time and rinsed with fresh water.

While shampoos have previously been disclosed which contain conditioningaids, they have not been totally satisfactory for a variety of reasons.One problem relates to compatibility problems between good cleaninganionic surfactants and the fatty cationic agents which are goodconditioning agents. This caused other surfactants such as nonionics,amphoterics and zwitterionics to be examined by workers in the field.Many of these efforts are reflected in patents issued in theconditioning shampoo area. See for example U.S. Pat. No. 3,849,348, Nov.19, 1974 to Hewitt; U.S. Pat. No. 3,990,991, Nov. 9, 1961 to Gerstein,and U.S. Pat. No. 3,822,312, Jul. 2, 1974 to Sato.

The use of these other surfactants solved many of the compatibilityproblems but still did not provide complete solutions in all areas. Forinstance, cationic conditioners may not deliver the desired level ofsoftness desired by users. Materials which can provide increasedsoftness include the silicones, both those which are soluble and thosewhich are insoluble in the shampoo matrix.

Silicones in shampoo compositions have been disclosed in a number ofdifferent publications. Such publications include U.S. Pat. No.2,826,511, Mar. 11, 1958 to Green; U.S. Pat. No. 3,964,500, Jun. 22,1976 to Drakoff; U.S. Pat. No. 4,364,817, Dec. 21, 1982 to Pader; andBritish Patent No. 849,433, Sep. 28, 1960 to Woolston. While thesepatents disclose silicone containing compositions, they also do notprovide solutions to all of the problems encountered in making a totallysatisfactory product. One such problem is that of keeping a dispersed,insoluble silicone material suspended and the total product stable. Avariety of materials have been included in silicone containing shampoosfor purposes of thickening and stabilization but totally satisfactorysolutions are lacking.

The ULTRAMULSION™ dispersions of the present invention are one solutionto many of the aforementioned problems. These unique dispersions aredistinct from other emulsions as will become apparent from the followingbackground information regarding emulsions. When a system consists of asingle liquid phase it is described as a solution. A system containingtwo or more liquid phases is described as a multiphase solution oremulsion. According to Becher, an emulsion is an unstable heterogeneoussystem in which the diameters of the dispersed droplets in generalexceed 1000 Å. Becher P. in "Emulsions, Theory & Practice", (P. Becher,Ed.) page 2, Rheinhold, N.Y., 1965.

A more comprehensive definition of an emulsion is advanced by Clayton:"An emulsion is a system containing two liquid phases, one of which isdispersed as globules in the other. The liquid which is broken up intoglobules is termed the dispersed or discontinuous phase, while theliquid surrounding the globules is known as the continuous phase ordispersing medium" Clayton, W., "The Theory of Emulsions and TheirTechnical Treatment", 4th Ed. page 1, the Blakiston Co., Philadelphia,1943. It is well accepted that, mechanical work is required to effect anemulsion, see Bancroft W. D., J. Phys. Phy. Chem., 17: 501 (1913).

According to Prince, an emulsion may be defined as a dispersion of two(or more) mutually insoluble liquids, one in the other. Because of thesurface tension forces at play between the two liquids, the dispersedphase consists of spherical droplets. Prince, L. M. in "MicroemulsionTheory & Practice", pg. 2, Academic Press Inc., New York, N.Y. (1977).See also Prince, L. M. in "Biological Horizons in Surface Science", pg.361, Academic Press Inc. (1973). Emulsions, are generally not stable andupon standing or after centrifuging tend to separate into two or morelayers.

The three definitions of emulsions set forth above share one commonattribute, that is, mechanical work must be put into the emulsionsdescribed in order to disperse one liquid in the other in the form ofdroplets. This mechanical work can be in the form of agitation,homogenization, ultrasonication, etc.

In contrast, dispersions of very small droplet sizes which are formedspontaneously without the input of any mechanical work are calledmicroemulsions. See Prince 1977, p. 3. Generally, two surfactants areused in forming microemulsions, i.e., a water soluble surfactant and aco-surfactant such as alcohol, where one phase of the microemulsion isgenerally water. Thus, dilution or adulteration of the dispersed phaseby the co-solvent generally accompanies microemulsion formation. Theratio of surfactant to dispersed phase in microemulsions is much higherthan that of emulsions. Microemulsions are further characterized asoptically clear or opalescent and when spun in a laboratory centrifugefor 5 minutes at 100 G's, the dispersion remains stable and does notseparate.

Thus, fine particle sizes, exceptional stability and rheologicalproperties that can be easily adjusted, distinguish microemulsions fromemulsions. Moreover, as of 1977, no microemulsions had appeared in whichone of the mutually insoluble liquids was not water. See Prince, page34, (1977). Such may be theoretically possible but exceedingly in commonand irrelevant to hair care products which must eventually disperse inwater.

It has been surprisingly found that certain ULTRAMULSION™ dispersions,i.e., those of the present invention, provide various hair products withimproved properties including conditioning, moisturizing, protecting,repairing, etc., attributed to their enhanced substantivity and thereservoir effect achieved by solubilizing various lipid or oil solublesubstances in the discontinuous silicone phase of the ULTRAMULSION™dispersion. As discussed in greater detail below, these uniquedispersions have properties in common with both emulsions andmicroemulsions.

It is thus an object of the present invention to provide ULTRAMULSION™dispersion based shampoo/conditioners, conditioners, protectants,treatments and styling products with enhanced substantivity whichcontain a reservoir of various ingredients for treating hair.

It is another object of the invention to provide a method formanufacturing the ULTRAMULSION™ dispersion based hair care products ofthe invention.

It is still another object of the invention to provide means fortreating, conditioning, styling, etc. hair with ULTRAMULSION™ dispersionbased hair care products.

It is a further object of the present invention to provide ULTRAMULSION™dispersion based hair care products wherein various lipid or oil solubleactives are released from the ULTRAMULSION™ dispersion coating onto thehair over an extended period.

It is also an object of this invention to provide an ULTRAMULSION™dispersion for water based hair care products without the need to resortto use of complex high energy processes during manufacture of the haircare products. One highly beneficial and unique property ofULTRAMULSION™ dispersions is their ability to be formulated into waterbased hair care products in the same manner and as easily as commonsurfactants.

These and other objects will become readily apparent from the detaileddescription provided below.

Unless otherwise indicated, all percentages and ratios herein are byweight.

SUMMARY OF THE INVENTION

As described above, the present invention relates to various hair careproducts containing stable dispersions of certain high viscositysilicones in certain surfactants; wherein:

a. the dispersed silicones, which are insoluble in said surfactant, areoriented by the surfactant such that when dispersed in water they areparticularly adept at forming oriented coatings on hair with enhancedsubstantivity, and

b. the particle size of the dispersed silicone is from between about 0.1and about 10 microns, with a particle size distribution such that frombetween about 80 and 95% of the dispersed silicone is within thisparticle size range. In certain embodiments, between 80-95% of twodispersed silicones is less than 1-2 microns in particle size. Thesestable dispersions are described as ULTRAMULSION™ dispersions, which,together with their physical properties, when contained in hair careproducts, provide these hair care products with distinctiveconditioning, moisturizing, protecting, etc. properties where the noncontinuous silicone phase functions as a reservoir for various hairtreatment substances.

As described above, the ULTRAMULSION™ dispersions of hair care productsof the present invention combine certain characteristics of emulsionswith certain features of microemulsions. That is, like emulsions, theyare two phase systems comprising a silicone dispersed in a continuous,surfactant phase, wherein the silicone is insoluble in the surfactant.Unlike emulsions, but like microemulsions, these dispersions are stable.Unlike microemulsions, but like emulsions, mechanical work is requiredto form ULTRAMULSION™ dispersions. Unlike microemulsions, but likeemulsions, these ULTRAMULSION™ dispersions are not formed spontaneously.Like emulsions, the ULTRAMULSION™ dispersions do not contain a cosolventcommonly found in microemulsions. Of course, the ULTRAMULSION™dispersions of the present invention can be easily dispersed in variousliquids such as water to obtain stable dispersions. These dispersions ofULTRAMULSION™ dispersions in water have excellent utility in varioushair care products.

While not wishing to be bound by theory, it is hypothesized that unlikeeither emulsions or microemulsions, the dispersed silicones of theULTRAMULSION™ dispersions of the present invention are uniquely orientedwith their polar moieties in one general plane and their hydrophilicmoieties in a plane approximately opposite that of the polar moieties.This orientation promotes stability as well as bonding between the polaror hydrophilic moieties and the hair substrate thereby effectingoriented, monolayer coatings of the silicone onto hair. These orienteddispersions of silicones have a surprising broad range of utility inhair care products as detailed in the various examples below.

The emulsifying effects of uncoiling of the silicone molecule with theoxygen moieties generally oriented in one plane distinct from that ofthe organo moieties as illustrated in FIGS. 1 and 2, are furthersubstantiated by the following references: Eur. Poly. J., 26: 654(1990); J. Chem. Phys., 49: 1398 (1965); J. Chem. Phys., 54: 5011(1971); J. Chem. Phys., 59: 3825 (1973); Macromolecules, 7: 229 (1974);Macromolecules, 11: 627 (1978) and "Rubber-Like Elasticity: A MolecularPrimer", J. Mark, New York, Wiley-Interscience (1988).

Methods of preparing polyorganosiloxane emulsions with an averageparticle size of less than about 0.3 microns and polyorganosiloxanemicroemulsions with an average particle size of less than about 0.14micron are described in U.S. Pat. No. 4,620,878. Preparation ofoil-in-water microemulsions are described in U.S. Pat. No. 4,146,499.Specific surface active compositions used as emulsifiers withdiorganopolysiloxanes to form transparent microemulsions are describedin U.S. Pat. Nos. 4,562,331 and 3,975,294. U.S. Pat. No. 3,433,780teaches the preparation of colloid silane suspensions. See also"Chemistry and Technology of Silicones", W. Noll, pp. 428 to 431 (1968);Journal of Society of Cosmetic Chemists, 25: 609-619 (1974) and Journalof Colloid & Interface Science, 44: 242-248 (1973).

Micellar dispersions, microemulsions, and transparent emulsions aredescribed in detail in the "Annals of the New York Academy of Science",Shulman & Montagne (1961); U.S. Pat. No. 2,356,205, "The Theory ofEmulsions & Their Technical Treatment", 5th Edition, 1954, U.S. Pat.Nos. 3,497,006; 3,506,070, 3,254,714 and 3,307,628. However, theaqueous-free ULTRAMULSION™ dispersions of silicones in surfactants asdescribed herein are neither taught nor suggested by the foregoingreferences.

For the purposes of the present invention:

a. stable is defined as follows; a dispersion of the ULTRAMULSION™dispersion in water when subjected to centrifuging in a 100 Genvironment for 5 minutes, less than about 10% by weight of theULTRAMULSION™ dispersion separates from the continuous water phaseand/or a substantial portion (i.e., >50%) of the dispersed phase resistsseparation. This latter definition is particularly applicable to higherviscosity silicones. See Table 2.

b. water-free means, that the ULTRAMULSION™ dispersion of silicone andsurfactant is substantially free from water.

c. solvent free means, that the ULTRAMULSION™ dispersion of silicone andsurfactant is substantially free from co-solvents such as ethanol,isopropanol, and the like.

d. oriented means, that the polar moieties of the "uncoiled"polydimethylsiloxane in the ULTRAMULSION™ dispersion are generallyaligned in one plane with the hydrophilic oil seeking moieties alignedin a second plane such as illustrated in FIG. 2.

e. monolayer means, that the monomolecular film of the ULTRAMULSION™dispersion of the present invention when dispersed in water is attractedto hair by secondary bonding force to form a substantive coatingthereon.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 illustrates the "coiled" molecular configuration proposed forpolydimethylsiloxanes.

FIG. 2 illustrates the proposed molecular configuration of orientedpolydimethylsiloxanes after ULTRAMULSION™ dispersion processing;

FIG. 3 illustrates schematically an ULTRAMULSION™ dispersion process ofthe present invention; and

FIGS. 4 and 5 illustrate that the ULTRAMULSION™ dispersions of thepresent invention produced via various high shear dispersing meanshaving particle size distribution of 80+% under 10 microns.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

Referring to the drawings, FIG. 1 illustrates the accepted "coiled"configuration advanced for polydimethylsiloxanes, wherein the methylmoieties are oriented outwardly while the oxygen moieties are orientedinwardly toward the axis of the coil or helix. This configuration doesnot readily promote, bonding between the oxygen moieties and compatiblesurfaces such as hair.

FIG. 2 illustrates the "uncoiled oriented" configuration proposed forpolydimethylsiloxanes that have been dispersed in the stable,ULTRAMULSION™ dispersions of the present invention, wherein the oxygenmoieties are generally oriented in one plane distinct from that of themethyl moieties. This proposed uncoiled oriented configuration appearsto support the unique and unexpected stability, bonding and enhancedsubstantivity properties of the ULTRAMULSION™ dispersions of the presentinvention, as evidenced by the various coating applications of theseULTRAMULSION™ dispersions to hair. See the Examples provided below.

FIG. 3 illustrates the ULTRAMULSION™ dispersion process of the presentinvention wherein a nonionic surfactant and a polydimethylsiloxane 1,substantially free from water and co-solvent, are mixed in vessel 2,provided with mixing means 3, heat source 4, and inert head space 5. Theheated and mixed surfactant-polydimethylsiloxane 6, is then subjected tohigh shear dispersion at an elevated temperature in dispersing means 7,to produce the ULTRAMULSION™ dispersion 8, of the present invention. Thehigh shear dispersion device (7) is typically selected from amongdevices manufactured by Ross, IKA Works, etc. Other energy sources suchas flow-through ultrasonic cells may be used as well.

FIG. 4 is a chart describing the particle size distribution of anULTRAMULSION™ dispersion of the present invention containing from about50 to 95% by weight nonionic surfactant and from about 5 to 50% byweight polydimethylsiloxane (2.5 million cs) produced in a continuousprocess with an IKA Works dispersing means, (high shear dispersing) withan inlet temperature of 140° C. and an outlet temperature of 210° C.

FIG. 5 is a chart describing the particle size distribution of anULTRAMULSION™ dispersion of the present invention containing from about50 to 95% by weight nonionic surfactant and from about 5 to 50% byweight polydimethylsiloxane (2.5 million cs) produced in a batch processwith a Ross M/E 100 LC dispersing means fitted with a 20 mesh screen,operated at a temperature from about 120° to 160° C.

For purposes of the present invention, the term silicone means a clear,colorless substance containing polydialkylsiloxane polymers with averagekinematic viscosities ranging from about 100,000 centistokes (cs) toabout 50 million cs, preferably from about 1 million cs to about 25million cs, more preferably from about 1.5 million cs to about 10million cs, and most preferably from about 2 million to about 5 millioncs. This definition intentionally includes the so-called "gum" siliconeshaving viscosities of 30 to 50 million cs. Certain high viscositypolydimethylsiloxanes having viscosities from about 2.5 million cs toabout 4 million cs are particularly preferred for the hair care productsof the present invention. Other polydimethylsiloxanes suitable for thepresent invention include "substituted" water insoluble silicones andmixtures of polydiorganosiloxanes and substituted water insolublesilicones. Specifically, water soluble silicones are excluded from theULTRAMULSION™ dispersions of the present invention. See also Tables 1and 2 below.

The viscosity of some silicones can be measured by means of a glasscapillary viscometer as set forth in Dow Corning Corporate Test MethodCTM0004, Jul. 20, 1970.

The silicone may be either a high viscosity polyalkyl siloxane asdescribed in detail below, a polyaryl siloxane, a polyalkylaryl siloxaneor a polyether siloxane copolymer. Mixtures of these silicones may alsobe used and are preferred in certain embodiments of the presentinvention.

The polyalkylaryl siloxanes that may be used include, for example,polymethylphenylsiloxanes having viscosities above 1 million centistokesat 20° C. Some of these siloxanes are available, for example, from theGeneral Electric Company, from Dow Corning, and/or from Rhone-Poulenc.

The polyether siloxane copolymer that may be used is, for example, apolypropylene oxide modified dimethylpolysiloxane although ethyleneoxide or mixtures of ethylene oxide and propylene oxide may also beused.

References disclosing suitable silicone fluids include U.S. Pat. No.2,826,551 to Green; U.S. Pat. No. 3,964,500 to Drakoff; U.S. Pat. No.4,364,837 to Padner and British Patent No. 849,433 to Woolston. All ofthese patents are incorporated herein by reference. Also incorporatedherein by reference is Silicon Compounds distributed by PetrarchSystems, Inc., 1984. This reference provides a very good listing ofsuitable silicone materials.

Silicone materials found especially useful in the present compositionsto provide good dry combing are silicone gums. Silicone gums describedby Petrarch and others including U.S. Pat. No. 4,152,416, May 1, 1979 toSpitzer et al., and Noll, Walter, "Chemistry and Technology ofSilicones," Academic Press, New York (1968). Also describing siliconegums are various General Electric Silicone Rubber Product Data Sheets.All of these described references are hereby incorporated herein byreference. "Silicone gum" materials denote high molecular weightpolydiorganosiloxanes having a viscosity up to about 50,000,000 cs.Specific examples include polydimethylsiloxane; polydimethylsiloxane;methylvinylsiloxane copolymer; polydimethylsiloxane;diphenylmethvinylsiloxane copolymer and mixtures thereof.

As noted above high viscosity polydimethylsiloxanes i.e., those above100,000 cs are preferred in this invention. Particularly preferred arepolydimethylsiloxanes having viscosities ranging from between about 2.5million cs and about 50 million cs.

The safety of polydimethylsiloxanes for use in these various products iswell documented. See Rowe et al., Journal of Industrial Hygiene, 30(6):332-352 (1948). See also Calandra et al., ACS Polymer Preprints, 17: 1-4(1976) and Kennedy et al., J. Toxicol. & Environmental Health, 1:909-920 (1976).

As noted above, the preferred polydimethylsiloxanes useful in the haircare compositions of the present invention are described aspolymethylsiloxanes with the chemical composition (CH₃)₃ SiO SiO(CH₃)₂!_(n) Si(CH₃)₃, wherein n is a whole number. These polydimethylsiloxaneshave viscosities ranging up to about 50 million cs., and are generallydescribed as having high molecular weight.

The particle size of the silicone in the ULTRAMULSION™ dispersions ofthe present invention can range from between about 0.1 and about 10microns. In a preferred embodiment of the present invention the particlesize of polydimethylsiloxanes in the ULTRAMULSION™ dispersion rangesfrom below 1 up to about 5 microns. The particle size distribution ofthe polydimethylsiloxanes in the ULTRAMULSION™ dispersions of thepresent invention generally range from between about 80% and about 95%of the particles under 10 microns. See especially FIGS. 4 and 5. In apreferred embodiment of the present invention, from between about 80%and about 95% of the particles are under 5 microns. See also Table 2.

An essential component of the ULTRAMULSION™ dispersion of the presentinvention is a surfactant. The surfactant, may be selected from any of awide variety of synthetic anionic, amphoteric, zwitterionic and nonionicsurfactants. The surfactants suitable for the purposes of the presentinvention must function as the continuous phase and contain thediscontinuous silicone phase.

Synthetic anionic surfactants can be exemplified by the alkali metalsalts of organic sulfuric reaction products having in their molecularstructure an alkyl radical containing from 8-22 carbon atoms and asulfonic acid or sulfuric acid ester radical (NOTE: included in the termalkyl is the alkyl portion of higher acyl radicals). Preferred are thesodium, ammonium, potassium or triethanolamine alkyl sulfates,especially those obtained by sulfating the higher alcohols (C₈ -C₁₈carbon atoms), sodium coconut oil fatty acid monoglyceride sulfates andsulfonates; sodium or potassium salts of sulfuric acid esters of thereaction product of 1 mole of a higher fatty alcohol (e.g., tallow orcoconut oil alcohols) and 1 to 12 moles of ethylene oxide ether sulfatewith 1 to 10 units of ethylene oxide per molecule and in which the alkylradicals contain from 8 to 12 carbon atoms, sodium alkyl glyceryl ethersulfonates; the reaction product of fatty acids having from 10 to 22carbon atoms esterified with isethionic acid and neutralized with sodiumhydroxide; water soluble salts of condensation products of fatty acidswith sarcosine; and others known in the art.

Zwitterionic surfactants can be exemplified by those which can bebroadly described as derivatives of aliphatic quaternary ammonium,phosphonium, and sulfonium compounds, in which the aliphatic radicalscan be straight chain or branched, and wherein one of the aliphaticsubstituents contains from about 8 to 18 carbon atoms and one containsan anionic water-solubilizing group, e.g., carboxyl, sulfonate, sulfate,phosphate, or phosphonate. A general formula for these compounds is:##STR1## wherein R² contains an alkyl, alkenyl, or hydroxyl alkylradical of from about 8 to 18 carbon atoms, from 0 to about 10 ethyleneoxide moieties and from 0 to 1 glyceryl moiety; Y is selected from thegroup consisting of nitrogen, phosphorous, and sulfur atoms; R³ is analkyl or monohydroxyalkyl group containing 1 to about 3 carbon atoms; xis 1 when Y is a sulfur atom and 2 when Y is a nitrogen or phosphorousatom; R⁴ is an alkylene or hydroxyalkylene of from 1 to about 4 carbonatoms and Z is a radical selected from the group consisting ofcarboxylate, sulfonate, sulfate, phosphonate, and phosphate groups.

Examples include:

4- N,N-di(2-hydroxyethyl)-N-octadecylammonio!-butane-1-carboxylate;

5-(S-3-hydroxypropyl-S-hexadecylsulfonio!-3-hydroxypentane-1-sulfate;

3-P,P-diethyl-P-3,6,9-trioxatetradecocylphosphonio!-2-hydroxypropane-1-phosphate;

3-N,N-dipropyl-N-3-dodecoxy-2-hydroxypropylammonio!-propane-1-phosphate;

3- N,N-dimethyl-N-hexadecylammonio-propane-1-sulfonate;

4-N,N-di(2-hydroxyethyl)-N-(2-hydroxydodecyl)ammonio!-butane-1-carboxylate;

3- S-ethyl-S-(3-dodecoxy-2-hydroxypropyl)sulfonio!-propane-1-phosphate;

3- P,P-dimethyl-P-dodecylphosphonio!-propane-1-phosphonate; and

5-(N,N-di(3-hydroxypropyl)-N-hexadecylammonio!-2-hydroxypentane-1-sulfate.

Other zwitterionics such as betaines are also useful in the presentinvention. Examples of betaines useful herein include the higher alkylbetaines such as cocodimethyl carboxymethyl betaine, lauryl dimethylcarboxymethyl betaine, lauryl dimethyl alpha-carboxyethylene betaine,cetyl dimethyl carboxymethyl betaine, lauryl bis-(2-hydroxyethyl)carboxymethyl betaine, stearyl bis-(20-hydroxypropyl)-carboxymethyl betaine,oleyl dimethyl gamma-carboxypropyl betaine, laurylbis-(2-hydroxypropyl)alpha-carboxyethyl betaine, etc. The sulfobetainesmay be represented by cocodimethyl sulfopropyl betaine, stearyl dimethylsulfopropyl betaine, lauryl dimethyl sulfoethyl betaine, laurylbis-(2-hydroxy-ethyl)sulfopropyl betaine and the like; amido betainesand amidosulfo betaines, wherein the RCONH(CH₂)₃ radical is attached tothe nitrogen atom of the betaine are also useful in this invention. Theamido betaines are preferred for use in some of the compositions of thisinvention. A particularly preferred composition utilizes an amidobetaine, a quaternary compound, a silicone, a suspending agent and has apH of from about 2 to about 4.

Examples of amphoteric surfactants which can be used in theULTRAMULSION™ dispersions of the present invention are those which canbe broadly described as derivatives of aliphatic secondary and tertiaryamine in which the aliphatic radical can be straight chain or branchedand wherein one of the aliphatic substituents contains from about 8 toabout 18 carbon atoms and one contains an anionic water solubilizinggroup, e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate.Examples of compounds falling within this definition are sodium3-dodecylamino-propionate, sodium 3-dodecylamino-propane sulfonate,N-alkyltaurines such as the one prepared by reacting dodecylamine withsodium isethionate according to the teachings of U.S. Pat. No.2,658,072, N-higher alkyl aspartic acids such as those producedaccording to the teachings of U.S. Pat. No. 2,438,091, and the productssold under the trade name "Miranol" and described in U.S. Pat. No.2,528,378.

Nonionic surfactants, which are preferably used in combination with ananionic, amphoteric or zwitterionic surfactant, can be broadly definedas compounds produced by the condensation of alkylene oxide groups(hydrophilic in nature) with an organic hydrophobic compound, which maybe aliphatic or alkyl aromatic in nature. Examples of preferred classesof nonionic surfactants are:

1. The polyethylene oxide condensates of alkyl phenols, e.g., thecondensation products of alkyl phenols having an alkyl group containingfrom about 6 to 12 carbon atoms in either a straight chain or branchedchain configuration, with ethylene oxide, the said ethylene oxide beingpresent in amounts equal to 10 to 60 moles of ethylene oxide per mole ofalkyl phenol. The alkyl substituent in such compounds may be derivedfrom polymerized propylene, disobutylene, octane, or nonane, forexample.

2. Those derived from the condensation of ethylene oxide with theproduct resulting from the reaction of propylene oxide andethylenediamine products which may be varied in composition dependingupon the balance between the hydrophobic and hydrophilic elements whichis desired. For example, compounds containing from about 40% to about80% polyoxyethylene by weight and having a molecular weight of fromabout 5,000 to about 15,000 resulting from the reaction of ethyleneoxide groups with a hydrophobic base constituted of the reaction productof ethylene diamine and excess propylene oxide, said base having amolecular weight of the order of 2,500 to 3,000 are satisfactory.

3. The condensation product of aliphatic alcohols having from 8 to 18carbon atoms, in either straight chain or branched chain configuration,with ethylene oxide, e.g., a coconut alcohol ethylene oxide condensatehaving from 10 to 30 moles of ethylene oxide per mole of coconutalcohol, the coconut alcohol fraction having from 10 to 14 carbon atoms.

4. Long chain tertiary amine oxides corresponding to the followinggeneral formula: ##STR2## wherein R₁ contains an alkyl, alkenyl ormonohydroxy alkyl radical of from about 8 to about 18 carbon atoms from0 to about 10 ethylene oxide moieties, and from 0 to 1 glyceryl moiety,and R₂ and R₃ contains from 1 to about 3 carbon atoms and from 0 toabout 1 hydroxy group, e.g., methyl, ethyl, propyl, hydroxy ethyl, orhydroxypropyl radicals. The arrow in the formula is a conventionalrepresentation of a semipolar bond. Example of amine oxides suitable foruse in this invention include dimethyl-dodecylamine oxide,oleyldi(2-hydroxyethyl)amine oxide, dimethyloctylamine oxide,dimethyldecylamine oxide, dimethyltetradecylamine oxide.3,6,9-trioxaheptadecyldiethylamine oxide,di(2-hydroxyethyl)-tetracylamine oxide, 2-dodecoxyethyldimethylamineoxide, 3-dodecoxy-2-hydroxypropyldi-(3-hydroxy-propyl)amine oxide,dimethylhexadecylamine oxide.

5. Long chain tertiary phosphine oxides corresponding to the followinggeneral formula: ##STR3## wherein R contains an alkyl, alkenyl ormonohydroxyalkyl radical ranging from 8 to 18 carbon atoms in chainlength from 0 to about 10 ethylene oxide moieties and from 0 to 1glyceryl moiety and R' and R" are each alkyl or monohydroxyalkyl groupscontaining from 1 to 3 carbon atoms. The arrow in the formula is againthe conventional representation of a semipolar bond. Examples ofsuitable phosphine oxides are: dodecyldimethylphosphine oxide,tetradecyl-dimethylphosphine oxide, tetradecyl-methylethylphosphineoxide. 3,6,9-trioxaoctadecyldimethylphosphine oxide,cetyldimethylphosphine oxide,3-dodecoxy-2-hydroxypropyl-di(2-hydroxyl)phosphine oxide,stearyldimethylphosphine oxide, cetylethylpropylphosphine oxide,cetyldiethylphosphine oxide, dodecyl-diethylphosphine oxide,tetradecyl-diethylphosphine oxide, dodecyldipropylphosphine oxide,dodecyldi(2-hydroxyethyl)phosphine oxide,tetradecyl-methyl-2-hydroxydodecyldimethylphosphine oxide.

6. Long chain dialkyl sulfoxides containing one short chain alkyl orhydroxy alkyl radical of 1 to about 3 carbon atoms (usually methyl) andone long hydrophosphinic chain which contain alkyl, alkenyl,hydroxyalkyl, or keto alkyl radicals containing from about 8 to about 20carbon atoms, from 0 to about 10 ethylene oxide moieties and from 0 to 1glyceryl moiety. Examples include octadecyl menthyl sulfoxide,2-ketotridecyl methyl sulfoxide, 3,6,9,-trioxooctadecyl 2-hydroxyethylsulfoxide, dodecyl menthyl sulfoxide, oleyl 3-hydroxypropyl sulfoxide,tetradecyl menthyl sulfoxide, 3-methoxytridecyl methyl sulfoxide,3-hydroxytridecyl methyl sulfoxide, 3-hydroxy-4-dodecoxybutyl methylsulfoxide.

Many additional nonsoap surfactants are described in McCUTCHEON'S,DETERGENTS AND EMULSIFIERS, 1979 ANNUAL, published by Allured PublishingCorporation which is hereby incorporated herein by reference.

Particularly preferred nonionic surfactants are nonionic poloxamersurfactants of block copolymers of ethylene oxide and propylene oxideranging from flowable liquids of varying viscosities, to paste, prillsand cast solids with molecular weights from 1,100 to 150,000. Suitablenonionic surfactants are manufactured and marketed by BASF Corporationunder the trademarks Pluronic. Particularly preferred nonionicsurfactants are Pluronic F-68, F-88, F-108 and Pluronic F-127. These aredescribed in a BASF brochure entitled "Pluronic and Tetronic BlockCopolymer Surfactant." These nonionic surfactants suitable for thepresent invention can be described by the following structure: ##STR4##where x, y and x' are whole numbers. Surprisingly, the nonionicsurfactants of choice for the ULTRAMULSION™ dispersions of the presentinvention are reported in the referenced brochure to have marginaldetergency, emulsification and wetting properties. See Tables 1 and 2.

As noted above, the preferred nonionic poloxamer surfactants useful inthe coating compositions of the present invention are described aspolyoxyethylene-polyoxypropylene block copolymers such as Pluronic F-68,F-88, F-108 and F-127 (BASF) which have molecular weights of at leastabout 1000 such as those described in U.S. Pat. Nos. 4,343,785,4,465,663, 4,511,563 and 4,476,107, the disclosures of which are herebyincorporated herein by reference.

Emulsions of various coating substances including polydimethylsiloxanesin various surfactants including nonionic surfactants are disclosed andclaimed in U.S. Pat. Nos. 4,911,927, 4,942,034; 4,950,479; 5,009,881;5,032,387; 5,057,306; 5,057,307; 5,057,308, 5,057,309; 5,057,310,5,098,711, 5,165,913 and 5,284,648. There is however, no teaching orsuggestion in these references that these high viscosity siliconeemulsions are stable nor that the "coating" substances are oriented asthey are in the ULTRAMULSION™ dispersions of the present invention.

The ratio of surfactant to silicone in the ULTRAMULSION™ dispersioncoating compositions of the present invention can range from betweenabout 400:1 and about 1:2. In a preferred embodiment of the inventionthe ratio of surfactant to silicone is from between about 25:1 and 1:2.See Tables 1 and 2.

The ULTRAMULSION™ dispersions of the present invention may be preparedas follows:

Generally, if not a liquid, the surfactant is first heated to atemperature at which it becomes a liquid. The silicone is then dispersedin the heated surfactant with various high shear dispersing means.

In one preferred method, the heated surfactant is mechanically stirredalong with the silicone, to form a pre-emulsion mixture in which thesilicone is uniformly dispersed in the surfactant in droplets of alarger size than desired for the ULTRAMULSION™ dispersions but smallenough to optimize the subsequent high shear dispersions. This mixtureis subjected to high-shear dispersions with a means such as theIKA-WORKS DISPAX-Reactor with at least one superfine generator,alternatively, a Ross Model M.E., 100 LC fitted with a 20 mesh screen ora ultrasonicator such as MEDSONIC XL2010 fitted with 800-C Flow Cell &800-21CT 3/4 inch flanged horn can be used.

Various ULTRAMULSION™ dispersions of the present invention are preparedand analyzed as described in detail in the examples below.

                  TABLE 1                                                         ______________________________________                                                  Example No.                                                                   1   2     3     4   5   6   7   8   9   10                          COMPONENT   % W/W                                                             ______________________________________                                        DIMETHICONE                                                                   viscosity-centistokes                                                         100,000     10    --    --  --  33  --  --  --  --  --                        600,00      --    10    --  --  --  33  --  --  --  --                        2,500,000   --    --    10  --  --  --  33  --  20  --                        4,000,000   --    --    --  10  --  --  --  33  --  20                        Poloxamer-188                                                                             --    --    --  --  --  --  --  --  80  --                        Poloxamer-338                                                                             90    90    90  90  --  --  --  --  --  80                        Poloxamer-407                                                                             --    --    --  --  67  67  67  67  --  --                        ______________________________________                                    

PROCEDURE

Examples 1-10 are formed as follows; the Poloxamer is heated to 70°-90°C. to melt the solid material. Once melted, the Poloxamer is stirredwith an overhead mixing blade. Dimethicone is added and the entire massis mixed to obtain a uniform dispersion while maintaining the melttemperature. The material is then transferred to the homogenizer, ROSShomogenizer, model M.E. 100LC, and homogenized for 0.5 to 1.5 hours at8000-10,000 RPM. The material is then cooled by a suitable coolingapparatus. The cooled material is then ready for use.

                  TABLE 1A                                                        ______________________________________                                                      Example No.                                                                   11    12     13     14   15                                                   % W/W                                                           ______________________________________                                        DIMETHICONE                                                                   2,500,000 cs.   10      10     10   10   --                                   4,000,000 cs.   --      --     --   --   10                                   LIPID SOLUBLES                                                                Octyldimethyl PABA                                                                             1.0    --     --   --   --                                   Vitamin E Acetate                                                                             --       2.0   --   --   --                                   Isopropyl Palmitate                                                                           --      --      1.0 --   --                                   Fragrance #17.92.3415 (IFF)                                                                   --      --     --    1.5  1.0                                 SURFACTANT                                                                    Poloxamer 338   89.0    88.0   89.0 88.5 89.0                                 ______________________________________                                    

PROCEDURE

Examples 11-15 are formed by adding the lipid soluble material to thedimethicone to solubilize; and a clear solution results. This solutionis then added to the previously melted Poloxamer held at from about 60°to 80° C. and mixed until uniform. The mixture is then homogenized in aROSS, model ME 100LC mixer for 0.5 to 1.5 hours at 8000-10,000 RPM. Thematerial is then cooled using any suitable cooling apparatus

Specific poloxamer/polydimethylsiloxane ULTRAMULSION™ dispersionssuitable for use with various hair care products were prepared andanalyzed as described in Table 2 below:

                  TABLE 2                                                         ______________________________________                                        Example            Particle Size Distribution (%)                             No.    Product     <1μ <2μ                                                                             <3μ                                                                             <4μ                                                                             <5μ                                                                             >10μ                         ______________________________________                                        16     67/33 Poloxamer                                                                           44     50   4    1    1.0  0                                      338/100,000 cs.                                                               Dimethicone                                                            17     90/10 Poloxamer                                                                           24     4    5    1    2    0                                      338/600,000 cs.                                                               Dimethicone                                                            18     90/10 Poloxamer                                                                            2     3    63   24   8    0                                      407/2,500,000 cs.                                                             Dimethicone                                                            19     90/10 Poloxamer                                                                           1.5    6    .51  43.5 14   0                                      407/4,000,000 cs.                                                             Dimethicone                                                            ______________________________________                                    

The discontinuous silicone phase of the ULTRAMULSION™ dispersion canalso contain a wide range of lipid soluble and/or lipid dispersible haircare ingredients ranging from proteins, to essential oils, to fragranceto protectants such as U.V. absorbers, to pesticides such as pyrethrums,to repellents such as N,N-diethyl-m-toluamide (DEET). These variousingredients in the silicone phase of the ULTRAMULSION™ dispersionperform their intended function in various hair conditioners,shampoo/conditioners, styling products etc. as though they are containedin a "reservoir" as they continue to be available at the ULTRAMULSION™dispersion containing-hair interface, as long as the ULTRAMULSION™dispersion coating remains substantive to the hair. The sustainedconditioning moisturizing, protecting, repairing, and like effects onhair obtained with these improved hair care products are discussed invarious examples below.

The hair care products containing the ULTRAMULSION™ dispersions of thepresent invention will contain a variety of essential components rangingfrom surfactants for cleaning, to various conditioning substances suchas various proteins and modified proteins, to styling materials such asresins etc. These are detailed in various Examples described below.

Water is an essential component of most shampoo/conditioners andconditioners of the present invention which contain one or more of thevarious ULTRAMULSIONS™ dispersions described above. The water in theseproducts is generally present at a level of from about 20% to about 95%,preferably from between about 60% and about 90%.

In addition these hair care products can contain a variety ofnonessential optional components suitable for rendering suchcompositions more acceptable. See Tables 3 to 6 below.

Such conventional optional ingredients are well known to those skilledin the art, e.g., preservatives such as benzyl alcohol, methyl paraben,propyl paraben and imidazolidinyl urea; cationic surfactants such ascetyl trimethylammonium chloride, lauryl trimethyl ammonium chloride,tricetyl methyl ammonium chloride, stearyldimethyl benzyl ammoniumchloride, and di(partially hydrogenated tallow)dimethylammoniumchloride; thickeners and viscosity modifiers such as diethanolamide of along chain fatty acid (e.g., PEG 3 lauramide), block polymers ofethylene oxide and propylene oxide such as Pluronic F88 offered by BASFWyandotte, sodium chloride, sodium sulfate, polyvinyl alcohol, and ethylalcohol; pH adjusting agents such as citric acid, succinic acid,phosphoric acid, sodium hydroxide, sodium carbonate, etc., perfumes;dyes; and, sequestering agents such as disodium ethylenediaminetetraacetate. Such agents generally are used individually at a level offrom about 0.01% to about 10%, preferably from about 0.5% to about 5.0%by weight of the composition.

The pH of the present compositions is not critical and may be in therange of from 2 to about 10. However, as set forth earlier, certainzwitterionic/quaternary compositions preferably have pH's of from about2 to about 4.

METHOD OF MANUFACTURE

The shampoo/conditioners and conditioners and various styling and hairtreatment products of the present invention can be made by mixing thematerials together and heating from about 70° C. to about 90° C. Themixture is mixed thoroughly for about 10 minutes at from about 70° C. toabout 90° C. before being pumped through a heat exchanger to cool it toambient temperature.

INDUSTRIAL APPLICABILITY

The shampoo/conditioners, conditioners and various hair treatmentproducts of the present invention are used in a conventional manner forcleaning conditioning and/or treating hair. From about 0.1 g to about 10g of a composition is applied to hair that has been wetted, generallywith water, worked through the hair and then rinsed out.

The following Examples further describe and demonstrate preferredembodiments within the scope of the present invention. The Examples aregiven solely for the purpose of illustration and are not to be construedas limitations of the present invention as many variations thereof arepossible without departing from its spirit and scope.

The following compositions are illustrative shampoo-conditioners of thepresent invention.

                  TABLE 3                                                         ______________________________________                                                             EXAMPLE NO.                                                                   20  21    22    23  24                                   COMPONENT              % W/W                                                  ______________________________________                                        Sodium Lauryl Sulfate  7.5   7.5   7.5 7.5 7.5                                Sodium Lauryl Ether Sulfate                                                                          5.0   5.0   5.0 5.0 5.0                                Lauramide DEA          5.0   5.0   5.0 5.0 5.0                                Cocoamidopropyl Beatine                                                                              1.0   1.0   1.0 1.0 1.0                                ULTRAMULSION ™ dispersion (from Table 1)                                   Example 2              1.3   --    --  --  --                                 Example 3              1.3   --    --  --  --                                 Example 4              --    1.3   --  --  --                                 Example 5              --    --    --  --  1.3                                Example 9              --    --    --  1.3 --                                 Preservative           qv    qv    qv  qv  qv                                 Citric Acid            0.4   0.4   0.4 0.4 0.4                                Sodium Chloride        0.3   0.3   0.3 0.3 0.3                                D.I. Water             qv to 100%                                             pH                     6.0   6.0   6.0 6.0 6.0                                ______________________________________                                    

These compositions are stable and deliver good conditioning to hair thatis washed with the compositions.

The following are two anionic shampoo compositions illustrative of thepresent invention.

                  TABLE 4                                                         ______________________________________                                                             Example No.                                                                   25     26                                                Component              % W/W                                                  ______________________________________                                        TEA C.sub.12 -C.sub.12 Alkyl Sulfate                                                                 15.0     --                                            NH.sub.4 C.sub.12 -C.sub.14 Alkyl Ether Sulfate                                                      --       1.9                                           Sodium C.sub.12 -C.sub.14 Alkyl Sulfate                                                              --       1.9                                           Cocamide MEA           3.0      1.5                                           ULTRAMULSION ™ dispersion (Table 1)                                        Example 3              3.0      --                                            Example 4              --       3.0                                           Cocoamidopropyl Betaine                                                                              1.5      1.5                                           Citric Acid            0.6      0.6                                           Sodium chloride        0.4      --                                            Color/Preservative/Fragrance                                                                         qv       qv                                            D.I. Water             q.s. 100%                                                                              q.s. 100%                                     ______________________________________                                    

These compositions are also stable and deliver good hair conditioning.Additional shampoo-conditioner examples of the present invention aredescribed in the following two tables:

                  TABLE 5                                                         ______________________________________                                                     Example Nos.                                                                  27   28     29     30   31   32                                  Component      % W/W                                                          ______________________________________                                        Ammonium Lauryl Sulfate                                                                      12.0   12.0   12.0 15.0 8.0  8.0                               Ammonium Laureth (3)                                                                         4.0    4.0    4.0  4.0  8.0  8.0                               Sulfate                                                                       Ammonium Xylene Sulfonate                                                                    2.2    2.2    3.0  --   --   --                                Cetearyl Alcohol                                                                             1.0    1.0    0.1  0.5  1.0  1.0                               Glycol Distearate                                                                             0.75  2.5     0.76                                                                               0.75                                                                               0.75                                                                               0.75                             Cocamide MEA   1.0    1.5    1.0  1.0  1.0  1.0                               ULTRAMULSION ™                                                             dispersion                                                                    Example 11     3.0    3.0    --   --   --   --                                Example 12     --     --     --   3.0  --   --                                Example 13     --     --     --   3.0  --   --                                Example 14     --     --     3.0  --   --   --                                Example 15     --     --     --   --   --   3.0                               Lauryl Trimethyl Ammonium                                                                    --     --      0.75                                                                               0.75                                                                              --   --                                Chloride                                                                      Tricetyl Methyl Ammonium                                                                     1.0    0.5    0.5  0.5  --   --                                Chloride                                                                      Tri C.sub.8-10 Methyl Ammonium                                                               --     --     --   --   2.0  --                                Chloride                                                                      Tri C.sub.13 Amine                                                                           --     --     --   --   --    2.00                             Color/Perfume/Preservative/                                                                  qv to 100%                                                     Water                                                                         ______________________________________                                    

                  TABLE 6                                                         ______________________________________                                                        Example Nos.                                                  Example Nos.      33     34     35   36   37                                  Components        % W/W                                                       ______________________________________                                        NH.sub.4 C.sub.12-14 Alkyl Sulfate                                                              --     16.0   8.0  16.0 8.0                                 NH.sub.4 C.sub.12-14 Alkyl Ether Sulfate                                                        --     --     8.0  --   8.0                                 TEA C.sub.12-14 Alkyl Sulfate                                                                   18.2   --     --   --   --                                  Cocamide MEA      3.0    1.0    3.0  1.5  1.0                                 Cetearyl Alcohol  --     1.0    --   --   1.0                                 Ethylene Glycol Distearate                                                                      --      .75   --   --    .75                                Sodium Hydroxide (50%)                                                                          0.6     .01   --   --   --                                  ULTRAMULSION ™ dispersion                                                  Example 3         2.0    --     1.9  --   --                                  Example 4         --     3.5    --   --   --                                  Example 6         --     --     --   2.0  --                                  Example 10        --     --     --   --   2.0                                 Water/Perfume/Preservative/Color                                                                qs to 100%                                                  ______________________________________                                    

The present invention has been described in detail, including thepreferred embodiments thereof. However, it will be appreciated thatthose skilled in the art, upon consideration of the present disclosure,may make modifications and/or improvements on this invention and stillbe within the scope and spirit of this invention as set forth in thefollowing claims.

What is claimed is:
 1. A hair care composition selected from the groupconsisting of shampoo/conditioners, conditioners, treatments and stylingaids wherein said product contains an aqueous-free high shear orULTRAMULSION™ dispersion, formed by heating a mixture of surfactant andsilicone, followed by high shear mixing wherein:a. the silicone isinsoluble in said surfactant, has a viscosity of greater than about100,000 cs and a mean particle size up to about 10 microns. b. thesurfactant to silicone ratio in the ULTRAMULSION™ dispersion is frombetween about 400:1 and about 1:1; and the surfactant has an orientingeffect on the silicone, c. the ULTRAMULSION™ dispersion forms stabledispersions in aqueous containing hair care compositions, and d. saidhair care composition exhibits enhanced substantivity to hair while thedispersed silicone phase of said ULTRAMULSION™ dispersion functions as areservoir for various lipid soluble and lipid dispersible hair treatmentingredients.
 2. A hair care product according to claim 1, wherein saidULTRAMULSION™ dispersions comprises a nonionic poloxamer surfactant andpolydimethylsiloxane wherein:a. said polydimethylsiloxane has thechemical composition (CH₃)₃ SiO SiO(CH₃)₂ !_(n) Si(CH₃)₃, wherein n is awhole number; b. said surfactant has the chemical composition ##STR5##wherein X, Y, and X' are whole numbers; c. the viscosity of thepolydimethylsiloxane ranges from between about 2.5 million and about 50million cs; d. the particle size of most of the polydimethylsiloxane inthe ULTRAMULSION™ dispersion is from between about 0.1 and about 10microns; e. substantially all of said polydimethylsiloxane particles inthe ULTRAMULSION™ dispersions are from between about 1 and about 10microns; f. the nonionic surfactant is apolyoxyethylene-polyoxypropylene block copolymer having a molecularweight from between about 1,100 and about 150,000; g. the ratio ofsurfactant to polydimethylsiloxane is from between about 400:1 and about1:2; and h. the ULTRAMULSION™ dispersion dispersed in water based haircare products is stable.
 3. A method of manufacturing ULTRAMULSION™dispersions suitable for hair care compositions said method comprising,heating said surfactant and silicone mixture in a heated, stirred vesselsubstantially free from water, followed by subjecting said mixture tohigh shear dispersion;wherein: a. the silicone is insoluble in saidsurfactant, has a viscosity greater than 100,000 and up to about 50million cs, and a particle size up to about 10 microns, b. thesurfactant to silicone ratio in the high shear dispersion is frombetween about 400:1 and about 1:1; and the surfactant has an orientingeffect on the silicone, c. the silicone is oriented, exhibits enhancedsubstantivity to surfaces in the oral cavity and functions as areservoir for various lipid soluble and lipid dispersible hair careactive ingredients.
 4. A method according to claim 3, wherein the heatedvessel is provided with an inert head of gas.
 5. A method according toclaim 3, wherein said high shear dispersing means is fitted with a smallorifice.
 6. A method according to claim 3 wherein said high sheardispersing means comprises ultrasonication means.
 7. A stable aqueousbased hair care composition containing an ULTRAMULSION™ dispersioncomprised of a nonionic poloxamer surfactant and a polydimethylsiloxaneinsoluble in said surfactant wherein:a. said polydimethylsiloxane hasthe chemical composition (CH₃)₃ SiO SiO(CH₃)₂ !_(n) Si(CH₃)₃, wherein nis a whole number; b. said surfactant has the chemical composition##STR6## wherein X, Y, and X' are whole numbers; c. the viscosity of thepolydimethylsiloxane ranges from between about 2.5 million and about 50million cs; d. the particle size of the polydimethylsiloxane in theULTRAMULSION™ dispersion is from between about 0.1 and about 10 microns;e. substantially all of said polydimethylsiloxane particles in theULTRAMULSION™ dispersions are from between about 1 and about 10 microns;f. the nonionic surfactant is a polyoxyethylene-polyoxypropylene blockcopolymer having a molecular weight from between about 1,100 and about150,000; g. the ratio of surfactant to polydimethylsiloxane is frombetween about 400:1 and about 1:2; and h. the ULTRAMULSION™ dispersiondispersed in water is stable.
 8. A hair care product according to claim7, wherein the ratio of said surfactant to said silicone is 9:1 and 90%of the silicone particles are from between about 1 and 3 microns.
 9. Ahair care product according to claim 7, wherein the ratio of saidsurfactant to said silicone is 2:1 and 100% of the silicone dispersionis less than 10 microns.
 10. A hair care product according to claim 7,wherein the ratio of said surfactant to said silicone is 1:1 and thesilicone particles in said ULTRAMULSION™ dispersion are less than 10microns.
 11. An aqueous based shampoo/conditioner containing anULTRAMULSION™ dispersion comprising a nonionic poloxamer surfactant andpolydimethylsiloxane insoluble in said surfactant wherein:a. saidpolydimethylsiloxane has the chemical composition (CH₃)₃ SiO SiO(CH₃)₂!_(n) Si(CH₃)₃, wherein n is a whole number; b. said surfactant has thechemical composition ##STR7## wherein X, Y, and X' are whole numbers; c.the viscosity of the polydimethylsiloxane ranges from between about 1.5million and about 4 million cs; d. the particle size of most of thepolydimethylsiloxane in the ULTRAMULSION™ dispersion is from betweenabout 0.1 and about 10 microns; e. from between about 80% and 95% ofsaid polydimethylsiloxane particles in the ULTRAMULSION™ dispersions arefrom between about 1 and about 10 microns; f. the nonionic surfactant isa polyoxyethylene-polyoxypropylene block copolymer having a molecularweight from between about 1,100 and about 150,000; g. the ratio ofsurfactant to polydimethylsiloxane is from between about 400:1 and about1:2; and h. the ULTRAMULSION™ dispersion dispersed in water basedshampoo/conditioner is stable.
 12. A hair care composition according toclaim 7, wherein the silicone is a polydimethylsiloxane uncoiled andoriented wherein the oxygen moieties are generally oriented in a planedistinct from that of the methyl/moieties.
 13. A hair care compositionaccording to claim 1, wherein the surfactant is selected from the groupconsisting of flowable liquids of varying viscosities, pastes, prillsand cast solids.
 14. A method according to claim 3, wherein the highshear dispersion is achieved with high shear dispersing means selectedfrom the group consisting of superfine dispersion means and ultrasonicdispersion means.
 15. A hair care composition according to claim 7,wherein the ratio of surfactant to polydimethylsiloxane is 1:1 and atleast 80% of the polydimethylsiloxane dispersed particles are between 1and 9 microns.
 16. A hair care composition according to claim 1, whereinthe ratio or surfactant to polydimethylsiloxane is 9:1 and about 90% ofthe polydimethylsiloxane dispersed particles are between 1 and 3microns.
 17. A hair care composition according to claim 1, wherein theratio or surfactant to polydimethylsiloxane is 2:1 and about 90% of thepolydimethylsiloxane dispersed particles are between 1 and 3 microns.18. A hair care composition according to claim 7, wherein the ratio ofsurfactant to polydimethylsiloxane is 4:1 and about 90% of thepolydimethylsiloxane dispersed particles are between 1 and 9 microns.19. A hair care composition according to claim 7, wherein the ratio ofsurfactant to polydimethylsiloxane is 9.5:0.5 and about 100% of thepolydimethylsiloxane dispersed particles are between 1 and 9 microns.20. A hair care composition according to claim 7, wherein thepolydimethylsiloxane has a viscosity of 2.5 million cs and thesurfactant is a solid at room temperature.